Unit 4 - Bonding

Ionic Compounds
- Ionic bond: electrostatic forces of attraction between oppositely-charged ions, formed
due to elements having a large difference in electronegativity
- Ionic character: determined by the difference in electronegativity. High difference = high
ionic character.
- Ionic compounds are arranged in a three-dimensional crystalline structure, known as an
ionic lattice.
- Charge density: the charge per unit volume of an ionic compound
- Melting and Boiling Points: Very High, as the electrostatic force of attraction between
the ions is very strong and requires high amounts of energy to break, which also causes
low volatility
- Solubility: Soluble in polar solvents like water, as ions are attracted to polar molecules
like water, and they dissociate and the lattice breaks down
- Conductivity: cannot conduct electricity in a solid state, as ions are firm and unable to
move, but they can in aqueous or molten states.
- Brittleness: Usually brittle, because of repulsive forces that are exerted when the ions
are forced next to each other.
- Ionic compounds with polyatomic ions have both covalent and ionic bonds. Atoms in the
polyatomic ions are covalently bonded, while two polyatomic ions are bonded ionically.

Covalent Compounds
- Covalent bond: electrostatic forces of attraction between the positively charged nucleus
and the shared pair of electrons, usually between non-metals
- Bond length: distance between two covalently bonded nuclei (in picometers (pm))
- Bond strength: the energy needed to break a covalent bond (in kJ/mol)
- Bond strength and length are inversely proportional: Higher bond length = lower bond
strength.
- Melting and Boiling points: relatively low melting and boiling points due to weak
intermolecular forces
- Solubility: Non-polar substances generally dissolve in non-polar solvents; Polar
substances generally dissolve in polar solvents
- Conductivity: no free ions, so they are not able to conduct electricity, but there are
exceptions, such as HCl
- Bonds can be single, double or triple
Lewis Dot Structures:
- Central atom must be of large size, or least electronegative, or least in number.
- Oxygen, sulfur, phosphorus, nitrogen, silicon, carbon, chlorine, iodine can all be central
atoms.
- The octet of the corner must be fulfilled first.
- A central atom can have 8 or more electrons(if expanded octet), but corner atoms can
only have 8.
- The central atom tries to remain in maximum covalency so it makes the maximum
number of covalent bonds it can form.
- If there is a positive charge it is always on the central atom while every negative charge
is on the corner atoms.

Coordinate covalent bonds differ from normal covalent bonds in the way that in a coordinate
bond, both the shared electrons are provided by the one of the atoms. Coordinate covalent
bonds also occur when one of the atoms in the molecule is electron-deficient, meaning that it
has less electrons in its valence shell and has an incomplete octet. It does not satisfy the octet
rule, and the elements are H, He, B, and Be. These atoms have the tendency to accept an
electron pair from a molecule with a lone pair.

Bond Order: The number of bonds between 2 atoms. Single bonds have a bond order of 1,
double have bond order of 2, and triple bonds have a bond order of 3.

Octet rule: the octet rule states that the most stable arrangement for an atom to have in its
outermost shell is 8 electrons. Atoms that have less than 8 electrons in their outermost shell
are said to be electron-deficient, and they may have to form coordinate covalent bonds in
order to satisfy the octet rule.

VSEPR Theory
● Electron domains consist of single, double, or triple bonds and lone pairs.
● There is repulsion between electron domains.
● The total amount of electron domains around the central atom of the molecule
determines the geometrical arrangement, or the electron domain geometry.
● The molecule’s shape is determined by the bond angle between the atoms bonded to
the central atom.
● Lone pairs have a higher concentration of charge as they are not shared between
atoms, and therefore their forces of repulsion are greater.
● Bond pairs (such as single, double or triple bonds) are shared electrons so the
concentration of charge is considerably lesser.
● In descending order of repulsion, the electron domains are:
○ Lone pair-lone pair > Lone pair-bond pair > Bond pair-bond pair
● Since a lone pair repels a bond pair more than a bond pair and bond pair, this reduces
the bond angle between the bonded atoms around the central atom.
● The molecule will always take the shape which will minimize repulsion between
electron domains.
 Resonance Hybrid Structures

● Resonance occurs when more than one valid Lewis structure can be drawn for a
particular molecule.
● This means that a certain bond(such as a double bond) has equal probability of being
in different places, and so each bond is in between a single and a double bond.
● The actual structure of this type of molecule is known as a resonance hybrid structure.
● Since in resonance hybrid structures the electrons are not confined to one location and
can take different locations, they are considered as delocalised and the molecule is
more stable.
● Some resonance hybrid structures include: C6H6 (benzene), O3 (ozone), CO32-

Allotropes of Carbon

Diamond
● Each carbon atom is bonded to 4
other carbon atoms in a tetrahedral
structure with repeated patterns.
● It is a giant covalent/network
covalent/macromolecular structure.
● High melting point and boiling point.
● Non-conductor of electricity as all the
electrons are bonded and cannot
move.
● Great thermal conductor.
● Extremely hard and brittle.
● Transparent crystal.
Graphite
● Each carbon atom is bonded to 3
other carbon atoms.
● Forms hexagonal structures
● Has many layers.
● It is a giant covalent/network
covalent/macromolecular structure.
● High melting point and boiling point.
● Good conductor of electricity due to
presence of mobile electrons.
● Not a good conductor of heat.
● Soft and slippery due to many layers
slipping over each other.
● Dark gray shiny solid.

Graphene Fullerene (C60)

● Each carbon atom is bonded to 3
other carbon atoms.
● Forms hexagonal structures with bond
angles of
● Has only one layer(two dimensional).
● Good electrical conductor.
● Best thermal conductor.
● High melting and boiling point.
● Almost fully transparent.
● Flexible and has high tensile strength.
● Used in photo-voltaic cells and many
electronic devices.
● Each carbon atom is bonded in a
sphere of 60 carbon atoms, consisting
of 12 pentagons and 20 hexagons.
● Semi-conductor due to some electron
mobility.
● Very low thermal conductivity.
● Low melting and boiling point.
● Flexible.
● Yellow, crystalline solid.
● Used in lubricants and
nano-technology.
 Giant Covalent Structures
- Giant covalent structures include diamond, graphite, silicon, and silicon dioxide (SiO2)
- They generally have high melting and boiling points, are very hard, insoluble in water,
and non-conductors of electricity

Silicon Silicon Dioxide(SiO2)

- Each silicon atom is bonded to 4 other
silicon atoms covalently in a
tetrahedral structure
- Poor conductor of electricity due to
low electron mobility.
- Extremely hard and brittle.
- High melting and boiling points.
- Each silicon atom is bonded to 4
oxygen atoms and each oxygen atom
is bonded to 2 silicon atoms in a
tetrahedral structure
- Non-conductor of electricity
- Very hard and brittle.
- High melting and boiling points.

Intermolecular forces

- Intermolecular forces refer to the forces that hold the molecules together.
- Intermolecular forces affect the physical properties such as volatility, solubility and
conductivity.

London (Dispersion) Forces

- Exist between all atoms and molecules.
- Consist of: Instantaneous or temporary dipoles and Induced dipoles
- London Dispersion forces are relatively weak and their strength depends on two factors:
- The polarizability of the molecule (ease with which temporary dipoles can be
formed), and the surface area of the molecule
- Part of Van der Waal’s forces with dipole-dipole forces.

Dipole-Dipole Forces
- Only exist in polar molecules as they have permanent dipoles.
- Molecules are attracted to each other due to the opposite charges of the permanent
dipoles.
- Greater in strength than London Dispersion forces.
- Part of Van der Waal’s forces with London Dispersion forces.

Hydrogen Bonding
- Occurs between polar molecules that contain an atom with a lone pair such as: O, N, F.
- The lone pair has a negative charge due to electrons whereas an atom of another
molecule has a permanent positive charge (δ+), and they attract, forming a hydrogen
bond.
- Strongest of the three.
- Leads to high melting and boiling points.
Metallic Bonding
- Electrostatic forces of attraction between a lattice of cations and a sea of delocalised
electrons
- The strength of the metallic bond depends on two factors: Charge on the metal ion
(higher = stronger) and ionic radius (bigger = weaker)
- Conductivity: good conductors of electricity and heat due to delocalized electrons for
efficient electrical and thermal conductivity
- Malleability/Ductility: they are because of the random movement of deloc. Electrons
- Melting and Boiling points: Very high due to strong electrostatic forces of attraction.
- Shiny/Lustrous: the delocalized electrons reflect light

Alloys
- Alloys are made by adding a metal element to another element in molten state. When
the homogenous mixture solidifies, the metal becomes very hard and the layers cannot
slide over each other easily.

Brass Bronze Mild Steel Stainless Steel

70% Cu, 30% Zn 90% Cu, 10% Sn 99.7% Fe, 0.3% C 74% Fe, 18% Cr, 8% Ni

Sigma bond
- Formed when two atomic orbitals overlap along the bond axis, in a head-on manner
- The electron density is concentrated between the nuclei of bonded atoms
- Sigma bonds are always present in any kind of bond (ie. single, double, triple)
Pi bond
- Formed when two p orbitals overlap sideways above and/or below the bond axis.
- The electron density is concentrated in two regions - above and/or below the plane of
the bond axis.
- Only forms alongside the formation of a sigma bond ie. only forms in a double or triple
bond
- A double bond contains one sigma and one pi bond; a triple bond contains one sigma
and two pi bonds.

Hybridization
- Defined as the process by which atomic orbitals within an atom mix to produce hybrid
orbitals of intermediate energy.
- Covalent bonds with hybridized orbitals are often stronger.

Excitation
- Formation of covalent bonds starts with the excitation of electrons
- eg. Consider carbon: it only has two singly paired electrons available for bonding
- In order to maximize bonding, an electron from the 2s orbital moves to the 2p orbital,
making four unpaired electrons free for bonding.
- This is known as excitation, and occurs in almost all elements., and the amount of
energy this requires is compensated by bond formation
Hybridizing orbitals
- After excitation, the atomic orbitals available for bonding are not all the same.
- Some are at a higher energy level and would form unequal bonds.
- To resolve this, the available orbitals mix to form new hybrid atomic orbitals that are
identical to each other, but different from the original orbitals.
- Hybridisation involves different numbers and types of orbitals
- The overlap of a hybrid orbital with any other kind of orbital always forms a sigma bond.

sp3 Hybridization
- Mixing of s orbital and 3 p-orbitals, which orient themselves at 109.5º, forming a
tetrahedron (e.g. C in CH4)

sp2 Hybridization
- Mixing of s orbital and 2 p-orbitals, which orient themselves at 120º, forming a triangular
plane. (e.g. C in C2H4)
- P-orbitals that did not hybridize are free to form pi bonds, and this hybridization occurs
for double bonds

sp Hybridization
- Mixing of 1 s-orbital and 1 p-orbital, which orient themselves at 180º, forming a linear
shape. (e.g. C in C2H2)
- P-orbitals that did not hybridize are free to form pi bonds, and this hybridization occurs
for triple bonds

Determining type of hybridization

- Molecular geometry informs us about hybridization.
- Tetrahedral = sp3
- Triangular planar = sp2
- Linear = sp